US5187032A - Solid polymer electrolytes - Google Patents
Solid polymer electrolytes Download PDFInfo
- Publication number
- US5187032A US5187032A US07/685,677 US68567791A US5187032A US 5187032 A US5187032 A US 5187032A US 68567791 A US68567791 A US 68567791A US 5187032 A US5187032 A US 5187032A
- Authority
- US
- United States
- Prior art keywords
- solid polymer
- polymer electrolyte
- poly
- electrolyte according
- crosslinked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- This invention relates to solid polymer electrolytes suitable for use with primary batteries, secondary batteries, electrochromic displays, electrochemical sensors, ion-tophoretic devices, capacitors and other electrochemical devices.
- thermoplastic polyethers such as high-molecular weight polyethylene oxide, three-dimensional cross-linked compounds of polyethers such as polyethylene oxide, and graft copolymers having linear polyethylene oxide side chains in backbone chains such as polyphosphazine chains, polysiloxane chains, polyethylene chains and polypropylene chains.
- Thermoplastic polyethers such as high-molecular weight polyethylene oxide and the above-mentioned graft copolymers both have low mechanical strength and their ion conductivity is also low at temperatures lower than room temperature.
- the mechanical strength and ionic conductivity at low temperatures of polyethers might be enhanced by crosslinking them into a three-dimensional network.
- Polyethers such as polyethylene oxide are capable of solubilizing large amounts of salts such as lithium perchlorate but they have a great tendency to form complexes with a lithium ion, causing crystallization through strong binding.
- the present invention has been accomplished under these circumstances and has as an object providing a solid polymer electrolyte that has improved ionic conductivity and mechanical strength.
- This object of the present invention can be attained by a solid polymer electrolyte that has an ionic salt in a three-dimensional crosslinked compound of a poly(vinylalkyl ether) represented by the following general formula: ##STR2## (where R is CH 3 , C 2 H 5 or CH(CH 3 ) (C 2 H 5 ); and n is an integer of 100-2,000).
- a poly(vinylalkyl ether) represented by the following general formula: ##STR2## (where R is CH 3 , C 2 H 5 or CH(CH 3 ) (C 2 H 5 ); and n is an integer of 100-2,000).
- poly(vinylmethyl ether) is used as the poly(vinylalkyl ether).
- the solid polymer electrolyte is composed of a three-dimensional crosslinked compound of poly(vinylalkyl ether) containing not only an ionic salt but also a compound that is capable of solubilizing said ionic salt.
- the solid polymer electrolyte is composed of the three-dimensional crosslinked compound that is crosslinked with a diacrylic acid ester compound and/or a dimethacrylic acid ester compound.
- the solid polymer electrolyte is compound of the three-dimensional crosslinked compound that is crosslinked by exposure to an ionizing radiation.
- Preferred but non-limiting examples of the ionic salt that can be used in the present invention include LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 6 , LiI, LiBr, LiSCN, NaI, Li 2 B 10 Cl 10 , LiCF 3 CO 2 , NaBr, NaSCN, NaClO 4 , KSCN, KClO 4 , MgCl 2 , Mg(ClO 4 ) 2 , (CH 3 ) 4 NBF 4 , (CH 3 ) 4 NBr, (C 2 H 5 ) 4 NClO 4 , (C 2 H 5 ) 4 NI, and (n-C 5 H 11 ) 4 NI.
- Preferred but non-limiting examples of the compound that is capable of solubilizing the ionic salt include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4,4-dimethyl-1, 3-dioxolane, ⁇ -butyrolactone, propylene carbonate, ethylene carbonate, butylene carbonate, sulfolane, 3-methylsulfolane, tert-butyl ether, iso-butyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, methyl diglyme, methyl triglyme, methyl tetraglyme, ethyl glyme, ethyl diglyme and mixtures thereof.
- Exposure to ionizing radiations is an efficient method of crosslinking.
- exemplary ionizing radiations include ⁇ -rays, X-rays, electron beams and neutron beams.
- Propylene carbonate (250 g) having 1 mol/l of lithium trifluoromethanesulfonate dissolved therein and 130 g of a 70% toluene solution of poly(vinylmethyl ether) were charged into a flask and refluxed at 120° C. to form a uniform solution. Toluene was then removed from the solution under vacuum. Subsequently, diacrylate represented by the formula (CH 2 :CHC(O)O) 2 C 6 H 12 was mixed as a crosslinking agent in such an amount that the weight ratio of poly(vinylmethyl ether) to diacrylate was 10:3.
- the mixture was cast to form a 100- ⁇ m thick film in a stainless steel petri dish, which was irradiated to a dose of 10 Mrad with electron beams at an acceleration voltage of 300 kV in a nitrogen atmosphere.
- the irradiated film was transparent and highly elastic and had high mechanical strength.
- the ionic conductivity of this film as measured by the Cole-Cole plot method was 5 ⁇ 10 -4 S cm -1 (25° C.).
- its rupture strength was measured by applying a load to the sample that was placed on the top of a stainless steel disk (5 mm ⁇ ). The film was found to have a strength of 32 kg/cm 2 .
- a film of solid polymer electrolyte was prepared by repeating the procedure of Example 1 except that lithium perchlorate was used in place of lithium trifluoromethanesulfonate.
- the film had an ionic conductivity of 1 ⁇ 10 -3 S cm -1 (25° C.) and a rupture strength of 30 kg/cm 2 .
- the thickness of the film was 100 ⁇ m.
- the solid polymer electrolyte of the present invention is composed of a three-dimensional crosslinked compound of poly(vinylalkyl ether) containing an ionic salt.
- This solid polymer electrolyte has improved ionic conductivity and mechanical strength and hence will offer great industrial benefits.
Abstract
Description
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2-100803 | 1990-04-17 | ||
JP2100803A JP2914388B2 (en) | 1990-04-17 | 1990-04-17 | Polymer solid electrolyte |
Publications (1)
Publication Number | Publication Date |
---|---|
US5187032A true US5187032A (en) | 1993-02-16 |
Family
ID=14283552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/685,677 Expired - Lifetime US5187032A (en) | 1990-04-17 | 1991-04-16 | Solid polymer electrolytes |
Country Status (2)
Country | Link |
---|---|
US (1) | US5187032A (en) |
JP (1) | JP2914388B2 (en) |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5254627A (en) * | 1993-01-07 | 1993-10-19 | Ford Motor Company | Electrically conductive polypyrroleamine polymer networks |
US5266422A (en) * | 1992-12-21 | 1993-11-30 | Board Of Trustees Operating Michigan State University | Branched polyhydroxyalkanoate polymer salt electrolytic compositions and method of preparation |
EP0625704A2 (en) * | 1993-04-09 | 1994-11-23 | Ciba-Geigy Ag | Extended use planar sensors |
EP0643434A1 (en) * | 1993-02-23 | 1995-03-15 | Yuasa Corporation | Cell and method of its manufacture |
US5417870A (en) * | 1993-02-10 | 1995-05-23 | Eniricerche S.P.A. | Solid, polyether-bases polymeric electrolyte |
US5419977A (en) * | 1994-03-09 | 1995-05-30 | Medtronic, Inc. | Electrochemical device having operatively combined capacitor |
US6025096A (en) * | 1990-08-27 | 2000-02-15 | Hope; Stephen F. | Solid state polymeric electrolyte for electrochemical devices |
US6245262B1 (en) * | 1993-02-26 | 2001-06-12 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such films and devices |
EP1107267A1 (en) * | 1999-03-23 | 2001-06-13 | Nisshinbo Industries, Inc. | Electrolyte composition for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor |
US20080058835A1 (en) * | 2006-06-22 | 2008-03-06 | Board Of Regents Of The University Of Nebraska | Magnetically coupleable robotic surgical devices and related methods |
US20090099634A1 (en) * | 2007-10-15 | 2009-04-16 | Atanasoska L Liliana | Conductive composite electrode material |
US20090105796A1 (en) * | 2007-10-19 | 2009-04-23 | Atanasoska L Liliana | Fibrous electrode material |
US20100318059A1 (en) * | 2003-07-08 | 2010-12-16 | Board Of Regents Of The University Of Nebraska | Robotic devices with agent delivery components and related methods |
US8679096B2 (en) | 2007-06-21 | 2014-03-25 | Board Of Regents Of The University Of Nebraska | Multifunctional operational component for robotic devices |
US8828024B2 (en) | 2007-07-12 | 2014-09-09 | Board Of Regents Of The University Of Nebraska | Methods, systems, and devices for surgical access and procedures |
US8894633B2 (en) | 2009-12-17 | 2014-11-25 | Board Of Regents Of The University Of Nebraska | Modular and cooperative medical devices and related systems and methods |
US8968267B2 (en) | 2010-08-06 | 2015-03-03 | Board Of Regents Of The University Of Nebraska | Methods and systems for handling or delivering materials for natural orifice surgery |
US8974440B2 (en) | 2007-08-15 | 2015-03-10 | Board Of Regents Of The University Of Nebraska | Modular and cooperative medical devices and related systems and methods |
US9010214B2 (en) | 2012-06-22 | 2015-04-21 | Board Of Regents Of The University Of Nebraska | Local control robotic surgical devices and related methods |
US9060781B2 (en) | 2011-06-10 | 2015-06-23 | Board Of Regents Of The University Of Nebraska | Methods, systems, and devices relating to surgical end effectors |
US9089353B2 (en) | 2011-07-11 | 2015-07-28 | Board Of Regents Of The University Of Nebraska | Robotic surgical devices, systems, and related methods |
US9498292B2 (en) | 2012-05-01 | 2016-11-22 | Board Of Regents Of The University Of Nebraska | Single site robotic device and related systems and methods |
US9579088B2 (en) | 2007-02-20 | 2017-02-28 | Board Of Regents Of The University Of Nebraska | Methods, systems, and devices for surgical visualization and device manipulation |
US9743987B2 (en) | 2013-03-14 | 2017-08-29 | Board Of Regents Of The University Of Nebraska | Methods, systems, and devices relating to robotic surgical devices, end effectors, and controllers |
US9770305B2 (en) | 2012-08-08 | 2017-09-26 | Board Of Regents Of The University Of Nebraska | Robotic surgical devices, systems, and related methods |
US9888966B2 (en) | 2013-03-14 | 2018-02-13 | Board Of Regents Of The University Of Nebraska | Methods, systems, and devices relating to force control surgical systems |
US10335024B2 (en) | 2007-08-15 | 2019-07-02 | Board Of Regents Of The University Of Nebraska | Medical inflation, attachment and delivery devices and related methods |
US10342561B2 (en) | 2014-09-12 | 2019-07-09 | Board Of Regents Of The University Of Nebraska | Quick-release end effectors and related systems and methods |
US10376322B2 (en) | 2014-11-11 | 2019-08-13 | Board Of Regents Of The University Of Nebraska | Robotic device with compact joint design and related systems and methods |
US10582973B2 (en) | 2012-08-08 | 2020-03-10 | Virtual Incision Corporation | Robotic surgical devices, systems, and related methods |
US10667883B2 (en) | 2013-03-15 | 2020-06-02 | Virtual Incision Corporation | Robotic surgical devices, systems, and related methods |
US10723835B2 (en) | 2015-01-12 | 2020-07-28 | Kinestral Technologies, Inc. | Electrochromic multi-layer devices with cross-linked ion conducting polymer |
US10806538B2 (en) | 2015-08-03 | 2020-10-20 | Virtual Incision Corporation | Robotic surgical devices, systems, and related methods |
US10966700B2 (en) | 2013-07-17 | 2021-04-06 | Virtual Incision Corporation | Robotic surgical devices, systems and related methods |
US11826014B2 (en) | 2016-05-18 | 2023-11-28 | Virtual Incision Corporation | Robotic surgical devices, systems and related methods |
US11883065B2 (en) | 2012-01-10 | 2024-01-30 | Board Of Regents Of The University Of Nebraska | Methods, systems, and devices for surgical access and insertion |
US11903658B2 (en) | 2019-01-07 | 2024-02-20 | Virtual Incision Corporation | Robotically assisted surgical system and related devices and methods |
US11950867B2 (en) | 2018-01-05 | 2024-04-09 | Board Of Regents Of The University Of Nebraska | Single-arm robotic device with compact joint design and related systems and methods |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5620810A (en) * | 1992-07-22 | 1997-04-15 | Valence Technology, Inc. | Solid, solvent-containing electrolytes and electrolytic cells produced therefrom |
US5300376A (en) * | 1992-09-15 | 1994-04-05 | The United States Of America As Represented By The Secretary Of The Army | Highly conductive electrolyte for use in an ambient temperature rechargeable lithium battery and ambient temperature rechargeable lithium battery including said electrolyte |
US5463179A (en) * | 1993-12-06 | 1995-10-31 | Chaloner-Gill; Benjamin | Solid electrolyte obtained by the polymerization of diacrylate monomer having a rigid alkane segment |
Citations (6)
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US4303748A (en) * | 1978-11-22 | 1981-12-01 | Agence Nationale De Valorisation De La Recherche (Anvar) | Electrochemical generators for producing current and new materials for their manufacture |
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1990
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-
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Patent Citations (6)
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Cited By (73)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6025096A (en) * | 1990-08-27 | 2000-02-15 | Hope; Stephen F. | Solid state polymeric electrolyte for electrochemical devices |
US5266422A (en) * | 1992-12-21 | 1993-11-30 | Board Of Trustees Operating Michigan State University | Branched polyhydroxyalkanoate polymer salt electrolytic compositions and method of preparation |
WO1994015376A1 (en) * | 1992-12-21 | 1994-07-07 | Michigan State University | Branched polyhydroxyalkanoate polymer salt electrolytic compositions and method of preparation |
USRE35257E (en) * | 1992-12-21 | 1996-05-28 | Board Of Trustees Operating Michigan State University | Branched poly(hydroxyalkanoate) polymer salt electrolytic compositions and method of preparation |
US5254627A (en) * | 1993-01-07 | 1993-10-19 | Ford Motor Company | Electrically conductive polypyrroleamine polymer networks |
US5417870A (en) * | 1993-02-10 | 1995-05-23 | Eniricerche S.P.A. | Solid, polyether-bases polymeric electrolyte |
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EP0643434A4 (en) * | 1993-02-23 | 1996-10-09 | Yuasa Battery Co Ltd | Cell and method of its manufacture. |
US6954300B2 (en) | 1993-02-26 | 2005-10-11 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such sold films, and processes for making such solid films and devices |
US6245262B1 (en) * | 1993-02-26 | 2001-06-12 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such films and devices |
EP1491883A1 (en) * | 1993-04-09 | 2004-12-29 | Novartis AG | Extended use planar sensors |
US6068748A (en) * | 1993-04-09 | 2000-05-30 | Berger; Joseph | Extended use planar sensors |
EP0625704A2 (en) * | 1993-04-09 | 1994-11-23 | Ciba-Geigy Ag | Extended use planar sensors |
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US5419977A (en) * | 1994-03-09 | 1995-05-30 | Medtronic, Inc. | Electrochemical device having operatively combined capacitor |
US5455999A (en) * | 1994-03-09 | 1995-10-10 | Medtronic, Inc. | Method for making electrochemical device |
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JP2914388B2 (en) | 1999-06-28 |
JPH03296556A (en) | 1991-12-27 |
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